Production of linear polyesters using triethanolamine as catalyst



United States Patent 3,475,379 PRODUCTION OF LINEAR POLYESTERS USING TRIETHANOLAMINE AS CATALYST Paul I-Iilaire, Lyon, Rhone, France, assignor to Societe Rhodiaceta, Paris, France, a French body corporate N0 Drawing. Filed Nov. 10, 1966, Ser. No. 593,288' Claims priority, application France, Nov. 18, 1965,

Int. (:1. C08g 17/013 US. Cl. 260-75 6 Claims ABSTRACT OF THE DISCLOSURE In the production of fibre-forming high linear polyesters, especially polyethylene terephthalates, by polycondensation of the corresponding bis-(w-hydroxyalkyl) terephthalates, triethanolamine is used as catalyst for the polycondensation in amount 10-500, preferably 50-250, parts by weight per million parts of the bis-hydroxyalkyl terephthalate reckoned as dimethyl terephthalate. When well known. Polyesters derived from terephthlic acid and l a glycol of the formula HO(CH ),,OH, in which n is an integer between 2 and 10, and more particularly polyethylene terephthalate, have proved particularly interest- Polyethylene terephthalate is obtained by' polycondensation, under reduced pressure and .at relatively high temperature, of bis-(B-hydroxyethyl)terephthalate (or an oligomer thereof, e.g. a dimer, trimer or tetramer obtained as the result of a limited degree of polycondensation).

This monomer is generally itself obtained by ester-inten' change between ethylene glycol and dimethyl terephthalate, though it may also be obtained by reacting terephtalic acid with ethylene glycol or ethylene oxide. All such reactions require the presence of a catalyst if they are to take place in a reasonably short time.

As catalysts, it has been proposed to employ metals or organic or inorganic derivatives thereof, both for the ester-interchange or ester formation and for the polycondensation. However, for catalysing the polycondensation, antimony oxide is usually employed, though it has the disandvantage that it is used as a powder which is rather sparingly soluble in the reaction mixture and mu be employed in relatively large quantities.

According to the present invention, poly-(polymethylice densation, but the polymers obtained are slightly coloured. In addition, it is known to use as ester-interchange catalysts tertiary amines such as trimethylamine, N-ethylmorpholine or N-cyclohexyldiethylamine, but these amines must be eliminated by evaporation before the polycondensation if a substantially colourless polymer iS to be obtained. It was therefore entirely unexpected that triethanolamine itself is both an effective polycondensation catalyst and leads to colourless polymers.

The melting point of triethanolamine is about 20-21 C. and it is preferably incorporated in the reaction mixture in liquid form. It is then perfectly miscible with the reaction mixture, and the quantity needed to exert a sufficient catalytic effect is very small, of the order of 10 to 500 parts by weight per million parts by weight calculated on the starting material (reckoned as dimethyl terephthalate); 50 to 250 parts per million are preferably used. i i

If the starting material is obtained by ester-interchange between a diester of terephthalic acid and a glycol, the

triethanolamine is added to the reactants when the esterinterchange reaction has ended. Generally, a conventional ester-interchange catalyst such as calcium acetate, manganous acetate or zinc acetate is employed. The polycondensation is carried out at the usual polycondensation temperatures, preferably between 270 and 290 C. The following examples illustrate the invention.

EXAMPLE 1-6 In Examples 1 to 6, which are summarised in Table I, the polycondensation is carried out as follows:

The ester-interchange.between 3,298 g. (17 mol) of dimethyl terephthalate and 2,635 g. (42.5 mol) of ethylene glycol is first carried out in a 10 litre round-bottomed glass flask, in the presence of an ester-interchange catalyst. After the methanol produced and excess ethylene glycol have been distilled off, the reaction mass is transferred into a 7.5 litre stainless-steel autoclave provided with a stirring system. There is then added tothe reactants, which are at a temperature of about 230 C., either triethanolamine in liquid form or (for comparison) antimony oxide in suspension in ethylene glycol and 0.5%

"by weight, calculated on the polymer tobe produced,"of

titanium dioxide also in suspension in ethylene glycol. The reaction mass is then heated to 250 C. with stirring at atmospheric pressure, while ethylene glycol is distilled ofi. The product is thereafter further heated from 250 C. to the temperature T chosen forthe polycondensation, while the pressure in the autoclave is gradually lowered to about 2.5 mm. Hg. Finally, in a last phase, referred to in Table I as the polycondensation phase, the pressure is further lowered to 0.2 mm. Hg, while the reaction mass is maintained at the temperature T. As may be seen from Table I, the duration of this latter phase varies with the nature and the quantity of the catalyst. Comparison of Examples 1 and 3 with. Examples 2 and....4 shows the advantage afforded by triethanolamine over antimony oxide; even though much less is used, the polycondensation phase goes more rapidly. In both cases, the number of terminal carboxyl groups and the softening point are very similar showing that the triethanolamine does not cause degradation of the polymer in spite of its high catalytic activity.

TABLE I Ester Interc hange catalyst Polycondens ation catalyst Polycondensaltion Characteristics of the polymer p ase Example No. Nature Amount 1 Nature Amount 1 'I., 0. Duration LV, 2 G.T. COOH 3 P.R., C.

1 Manganous acetate... 108 Triethanolamine 50 285 1 h. 20 min 0. 66 32 261 2. .do 108 SbgO 340 285 1 h. 50 261 Calcium acetate 180 Trietha 285 1 h. .35 262 do 180 SbzOs 340 285 1 h. .28 262 54 Tricthanolamine 10 275 1 h. 33 261. 5 54 SbgOg 170 275 1 h. 33 B61. 5

1 Parts per million by weight of metal (Mn, Sb, Ca, Zn) or of trimethanolamine calculated on the dimethyl terephthalate. 2 I.V.=intrins1c viscosity determined at 25 C. on a 1% by weight per volume solution of polymer in o-chlorophenol. 3 G.T. COOH=numher of terminal groups COOH per ton of polymer. (w5;)1).R.=Soitening point measured by penetromctry (the principle of determination is described by 0.B. Edgar dz E. Ellery J. Chem. Soc. 2033-2638 In Examples 7 to 10, which are summarised in Table II, and stretched by 3.6 times, had a tenacity of 4.60 g.p.d.

the polycondensation was carried out by the same proand an elongation of 24%. cedure as in Examples 1 to 6, but in a 50 litre autoclave, I claim: 111 the presence of 0.5% by weight, calculated on the 1. Process for the production of high linear fibre formpolymer, of titanium dioxide in suspension in glycol and ing poly-(polymethylene)terephthalates by polycondensphosphorous acid, at 285 C. ing bis-(w-hydroxyalkyl)-terephthalates and their oli- It will be seen from Table II that the duration of the gomers, which comprises the improvement of carrying out polycondensation and the characteristics of the polymer the polycondensation in the presence of triethanolamine vary only slightly as a function of the quantity of trias a catalyst therefor in amount 10-500 parts by weigat ethanolamine introduced. In addition, the presence of of triethanolamine per million parts of starting maternal phosphorous acid has no appreciable eifect on the char- 25 reckoned as dimethyl terephthalate. acteristics (intrinsic viscosity, terminal carboxyl groups, 2. Process according to claim 1, wherein 50-250 parts softening point) of the polymer, although the duration of per million of triethanolamine are used. the polycondensation phase is slightly increased. 3. Process according to claim 1, wherein the bis- TABLE II Ester-Interchange catalyst Polyeondensation catalyst Duration of Characteristiw of the polymer HHPOQ. the polycon- Example No. Nature Amount 1 Nature Amount 1 Content densation 1.V. G.T. COOH P.R., C!

7 Calcium acetate 180 Triethanolamine- 50 0. 024 2 h. min 0. 68 26 259. 5 d 180 do 100 0.042 2 h. 25 min. 0. 68 c 260 250 0. 024 2 h. 07 min 0.68 22 .262. 5 500 0. 024 2 h. 20 min 0.68 23 261 12 34 See footnotes in Table I. 6 Percentage by weight calculated on the dimethyl terephthalate.

The polymers obtained by the process of the invention terephthalate used as starting material is made by an are very white and possess in particular very high thermal ester-interchange reaction, and the triethanolamine is stability, as high as that of the polymers obtained with added to the reaction mixture between the ester-interantimony oxide. change and the polycondensation.

Comparative tests by thermal treatment at 185 C. in 4. Process according to claim 1, wherein the triethanolair for 10 hours were carried out on polymers obtained amine is added to the reaction composition as a liquid. with antimony oxide and polymers obtained by the proc- 5. Process according to claim 1, wherein the polyconess of the invention as shown in Examples 7 to 10 in densation is effected at a temperature of 270-290 C. Table II, and the results obtained are set out in Table III. 6. Process for the production of high linear fibre form- TABLE III Ester-Interchange Catalyst Polycondensation catalyst Before thermal treatment After thermal treatment Variation of the character- 1 l 1 X istics of the polymer Nature Amount Nature Amount 1 I.V. 2 G.T. COOH 3 LV. 2 G.T. COOH a A LV. A G.T. COOH Calcium acetate 180 Triethanolamine 0.68 26 0.68 29 0 3 Do 180 -.do 100 0.68 25 0.07 20 0. 01 4 Do 180 do- 250 0.68 22 0. 65 2s 0. 03 a Do... 180 0 500 0.68 23 0. as 24 0 1 D0 180 smo 340 0.07 25 0.65 20 0.02 4

l 2 a See footnotes in Table I and II.

Nitrogen determinations were also made on the polying poly-(polymethylene)-terephthalates, which comprises mers with a precision of 10%, and these proved that all making a bis-(w-hydroxyalkyl)terephthalate by an esterthe triethanolamine introduced is to be found in the interchange reaction, adding thereto as a polycondensapolymer. Despite this, the polymers are colourless, as altion catalyst 10-500 parts by weight of liquid triethanolready mentioned. Table IV summarises these results. amine per million parts of the terephthalate reckoned as TABLE IV dimethyl terephthalate, and heating the mixture until a Triethanohmine Triethanolamine linear polyester has been formed by polycondensation.

introduced found by analysis Amount, Amount References Cited 100 110 UNITED STATES PATENTS 228 2,363,581 11/1944 Frosch.

2,437,232 3/ 1948 Rothrock et al. H I See footnote at end of Tables I, II, and

Finally, spinning and stretching tests have shown that WILLIAM SHORT Pnmary Exammer yarns having normal characteristics are obtained from LOUISE P. QUAST, Assistant Examiner the polymers obtained by the process of the invention.

Thus, for example, a yarn having a count of 45 denier, US. Cl. X.R.

22 filaments, spun at 285 C. at a speed of 900 m./min. 260-475 

